Activity origin and design principles for atomic vanadium anchoring on phosphorene monolayer for nitrogen reduction reaction

Conversion of inert N₂ molecules into NH₃ via electrochemical methods is an environmentally friendly alternative to replace the traditional Haber-Bosch process. However, the development of highly efficient catalyst is still challenging. Herein, we report a density functional theory (DFT) based high-throughput screening to investigate the potential of 23 atomic transition metals (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, W, Pt and Au) supported on phosphorene monolayer as electrocatalyst for nitrogen reduction reaction (NRR). Our theoretical results demonstrate that V single atom anchoring on phosphorene monolayer exhibits good thermal stability, selectivity and excellent catalytic activity with a low overpotential of 0.18 V. Importantly, rational design principles and electronic descriptor between the intrinsic electronic properties and activation barrier have been developed. Our work offers a new promising noble metal-free catalyst for NRR and reveals profound insights into the activity origin to guide further design.